Method of preparing phenyl phenols



Patented is, 15, 19 p I 1,959,283

sArEs PANT METHOD OF PREPARING PHENYL PHENOLS Edgar C. Britton, Midland, Mich., assignor to The Dow Chemical Company, Midland, Mich, a corporation of Michigan No Drawing. Application March 2, 1931,

I Serial No. 519,692

12 Claims. (01. 260-154) The present invention concerns methods for one or two hours or more if necessary to obtain the preparation of phenols and particularly the desired conversion, such hydrolysis being relates to methods for preparing phenyl phepreferably carried out in contact with extensive nols by hydrolyzing the correspondin monocopper surfaces. The so obtained reaction mixhalo-diphenyls. V ture is then treated in any suitable way to iso- 60 It has been thought heretofore that the alkalate and recover the separate constituents thereline hydrolysis of a halogenated aromatic hydro- F i st the cooled or h t r a t m xcarbon always yields the corresponding phen l, ture may be extracted with a water-immiscible in which the hydroxy group occupies the same solvent such as benzene, chlorobenzene, carbon position as the halogen which it replaced, Howtetrachloride, or equivalent thereof, to remove 05 ever, in my copending application, Serial N caustic-insoluble ethers formed as by-products 519,693, filed March 2, 1931, I have disclosed that in the reaction, d p y x d whi h this rule does not obtain in the ca e i of h may then be recovered by'distillation of the solhalogenated aromatic hydrocarbons in which the t therefrom- The residual aqueous Solution 7 l5 aromatic nucleus is substituted by another hydromay then b treated to recover the phenyl phenol 70 carbon group,i. e., an alkyl or aryl group. E therefrom as such or in the form of a salt therer amples of such substituted hydrocarbons are the ealkali-metal 0 al iart metal Salt. chloro-toluenes and chloro-diphenyls." The hy- For instance, such aqueous solution may be acididrolysis of such compounds results in the forma- Tied With any Suitable a d, a hyd och o ic 0r tion of a mixture of isomeric phenols, instead Sulfuric acid, and thereby precipitated 75 I of a single phenol corresponding to th halogephenylphenol separated from residual liquors and nated hydrocarbon used in the reaction. Such fractionally distilled Otherwise pu mixtures of course require further treatment for Similar results can he Obtained by hydrolyzing separating the components, which is oft nti other substituted halo-hydrocarbons, such as a disadvantage when it is desired to produce only, r napht h t lu or th r so a single phenol product, 1 spending promo compounds. Further, a mixture I have now found that such formation of mixof su a a d d arb such as a tures of isomeric phenols may be pre e t d by mixture of mono-halogenatedisomers obtainedin carrying out'the hydrolysis in the presence of the halogenation of a substituted hydrocarbon, catalytically active metallic copper or copper 8 miXtllre 0f and pamwhlorodicompounds, and in general at a lower'temperaephehyls, can be hydrolyzed Similarly in the P sture than that required in the absence of such enoe of copper to form a mixture of the p t d catalyst. For example, when ortho-chlorodiy y Compoundsphenyl is hydrolyzed by heating under pressure The following examples illustrate several ways 35 with an aqueous alkali at a temperature between of carrying Out my invention.

300 and 400 C., the reaction, product contains a mixture of ortho-and meta-phenyl phenols. Example 1 However, if the reaction is carried out in contact A charge of 1.6 moles of ortho-chlorodiphenyl, with a suita pp r containing atalyst; ortho- 3.2 moles of sodium carbonate, and 3.05 kilograms 40 Phenyl phenol alone is P The following of water, was heated to 360 in a rotating copper description sets forth in detail the improved bomb in one-half hour, and maintained at said method constituting my invention, showing varitemperature for two hours. The reaction mixture 1 W y in W c the principle o e V t O was removed from the bomb, acidified with hydromay be used. chloric acid, and the precipitate separated from 5 'In general, my invention may be carried out residual liquors and then redissolved in sodium v as follows:Chlorodiphenyl, as represe a hydroxide solution. The alkaline solution was substituted halogenated aromatic hydrocarbon, is filtered from di-orthodiphenyl ether, and the mixed with a moderate excess of aqueous Sodium aqueous alkaline filtrate acidified with hydrohydroXlde 0f approXimetely 3 to 25 Per Cent chloric acid, thereby precipitating ortho-phenyl- 50- strength, in a proportion of a ut 1.5 to 5 moles phenol which was separated therefrom and disof said base per one mole of chlorodiphenyl, and tilled under reduced pressure. In such manner the mixture heated under pressure in a suitable there was obtained a 96 per cent conversion of apparatus, e. g. an autoclave, bomb, or tubular chloro compound into hydroxy compound, and autoclave system, at a temperature in general ortho-phenylphenol in approximately a '75 per 55 between about 250 and 350 C. for approximately cent yield of very pure product melting at 56.4 C.

The above ether, after one recrystallization from chlorobenzene, method at 116 0., and was obtained in a 73 gram yield.

Example 2 Similarly as in the above example, a mixture of 0.5 mole para-chlorodiphenyl, 1 moleof sodium carbonate, and 954 grams of water, was reacted in a rotating bomb with an electrically insulated internal copper cage therein, at 300 to 310 C.

for five hours. The reaction mixture was worked up similarly, thereby obtaining a practically quantitative conversion, and an 83 percent yield of substantially pure para-phenylphenol (m. p. 164 C.) and 10 grams of di-para-diphenyl ether. Example 3 As above described, a charge of 0.366 mole of ortho-chlorodiphenyl, 0.73 mole of sodium car bonate, and 690 grams of water was reacted at 360? C. for one hour in-an iron reactor internallycoated with copper, thereby obtaining a 98 per cent conversion. Ortho phenylphen'ol (m.,p. 56.5

C.) was isolated in a 65 per cent yield. 12 grams 30f di-orthodiphenyl ether was obtained as a byproduct.

Example 4 Similarly, 0.62..mo1e of ortho-chlorodiphenyl {and 700 grams of 10 per cent aqueous'sodium hydroxide solution was reacted at 350 to 360 C. for one-half hour in an iron reactor, internally copper-coated, a practically quantitative conversion being obtained. The. isolated ortho-phenylphenol (freezing point of 58.5

.C.) amounted to an per cent yield.

Example 5 A charge of 1 moleof alpha-chloronaphthalene (containing 3 per cent of the beta modification) 3.2 moles of sodium carbonate,fand 3 .05"'kilograms of water reacted at 300 C; for two'hou'rs in a copper reactor thereby obtaining a 94.3 per cent conversion. The crude reaction product was acidified, the solids separated therefrom, and such solids fractionally distilled, thereby obtaining 1 60.2gram's of alpha-naphthol 1(9'7Lper cent pure). and 64.7 grams of dinaphthyl ethers.

Example 6 described improved hydrolytic method, there may be used an alkali-metal hydroxide, carbonate, or

boratefor a mixture of two or more of such agents, or other equivalent thereof. Theconditions for carrying out such hydrolysis, such as the tempera: ture, duration of heating, concentration of hydrolytic base, etc; may be modified according to thehalo-hydrocarbon to be reacted, e. g. chloronaphthalene, chlorotoluene, 'or chlorocymene. In

general, the hydrolysis begins at approximately,

200C. or slightlyv above, the reaction proceeding more rapidly with increasing temperature. ,The

hydrolysis, which is quiteapparent at about 250 C., becomes effectivelyuseful at temperatures and 3.05 ,kilop. 34 C.) based between approximately 275 and 350 C., higher temperatures usually being unnecessary. Furthermore, my present invention results in the formation of pure ethers as by-products, whereas by the ordinary hydrolysis of the starting materials, mixed ethers and a mixture thereof are obtained.

By the expression copper-containing catalyst -in the claims, I mean a material acting catalytically, in the herein described hydrolytic process, such'material to include metallic copper, a copper compound, e..g. cuprous oxide, or a mixture of two or more of such components. Moreover,

such]catalyticmaterial is to be present in an availablefform. For instance, if metallic copper is to'be used as catalyst in a steel bomb, said metallic ,copper. is to. be. electrically insulated therefrom" to prevent deterioration or destruction of both the catalyst and the container, as disclosed in ace-pending application by John J. Grebe, ria No-..-e .6tad, A ri 2. 0 ;;P e 1,814,796.

Other modes of applying the principle of my invention may be employed instead of those explained, change being made as regards the details herein disclosed, provided the details stated byfanyoffthe following claims or the equivalent thereofjbe employed.

I thereforeparticularly point out and distinctly claim as my inventionz 1. The method of making froma halogenated diphenyla phenyl-phehpl wherein the hydroxy grouploccupies the original .pos iti on of the haloen. whi h ris slr eetm c h l ed diphn l w h a h d olyti f a entv und r, pressure in the presence .offa. copper-containing catalyst. 2. .The method of making from a halogenated diphelrlylv a phnylphenol wherein the hydroxy.

groupoccupies the original position of the, halo- 1 gen, .which comprises reacting such halogenated diphenyl with an aqueoushydrolytic agent from the groupiconsisting of an alkali-metalhydroxide,

Carbbmfie, Wel d m xt e f s h ents...

under pressureat a temperature of approximate- I t 36020- .i ep s n -o wner-containing catalyst.

3. The methodofimaking, from a chlorinated h ny l r y heno w er n th h r y group occupiesthe original position of the chlorine which comprisesreacting suchchlorinated diphehyl with; an' aqueous alkali metal base undenpressure ,at a temperaturepf approximately 250, to 360ffC. in the-presence of copper.

4. The method of makingfroma chlorodiphenyl a phenylphenol wherein the hydroxy grouppccupies the original comprises reacting ous sodium hydroxide under pressure at a temposition of the chlorine, which suchchlorodiphenyl with aque peratureof approximat l 250 to 360 0. in the f presence of copper. The hQd 9 m in whichv comprises reacting ortho-chlorodiphenyl w en aqueous hydrolytic agent under pressure at a temperature of approximately 250 to 360 C. in the presence of a copper catalyst.

which comprises reacting ortho-chlorodiphenyl with aqueous, sodium hydroxide under. pressure 6. The method of making ortho-phenylphenol n at a temperature :of approximately 250 to 360 C. in the presence of metallic copper.

7. The me thod oi making orthoephenylphenol which comprises reacting ortho chlorodiphenyl g with a hydrolytic agent from the :group consist: ing of an alkali metal; hydroxide, carbonate, borate and,rinixtures of such agents, in the presence ortho-p h enylpheno1 of copper and separating ortho-phenylphenol from the crude reaction mixture.

8. The method of making para-phenylphenol which comprises reacting para-chlorodiphenyl with an aqueous hydrolytic base under pressure at a temperature of approximately 250 to 350 C., in the presence of a copper catalyst.

9. The method of making para-phenylphenol which comprises reacting para-chlorodiphenyl with aqueous sodium hydroxide under pressure at a temperature of approximately 250 to 350 C., in the presence of metallic copper.

10. The method of making para-phenylphenol which comprises reacting para-chlorodiphenyl with a hydrolytic agent from the group consisting of an alkali-metal hydroxide, carbonate, borate and mixtures of such agents, in the presence of copper and separating para-phenylphenol from the crude reaction mixture.

para-phenylphenols from the crude reaction plOdllCt.

EDGAR C. BRITTON. 

